Fluorescent monomers and tagged treatment polymers containing same for use in industrial water systems

ABSTRACT

Fluorescent monomers are described and claimed which are synthesized by reacting a substituted or non-substituted naphthalic anhydride with an amine and with a moiety containing a polymerizable group. Such monomers are useful for the preparation of tagged treatment polymers. Such tagged treatment polymers are useful as scale inhibitors in industrial water systems.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

[0001] This patent application is a continuation-in-part patentapplication of U.S. patent application Ser. No. 09/560,881 FLUORESCENTMONOMERS AND TAGGED TREATMENT POLYMERS CONTAINING SAME FOR USE ININDUSTRIAL WATER SYSTEMS, filed Apr. 27, 2000, now allowed.

FIELD OF THE INVENTION

[0002] This invention relates to fluorescent monomers. In anotheraspect, this invention relates to tagged treatment polymers that containthese fluorescent monomers. In a further aspect, this invention relatesto the use of tagged treatment polymers containing fluorescentmonomer(s) therein in industrial water systems.

BACKGROUND OF THE INVENTION

[0003] In many industrial water systems that employ polymers as watertreatment agents it may be desirable to tag or mark such polymers tofacilitate monitoring thereof. By the term “monitoring” is meant hereinany type of tracing or tracking to determine the location or route ofthe polymers, and any type of determination of the concentration oramount of the polymer at any given site, including singular orintermittent or continuous monitoring. For instance, it may be desirableto monitor water treatment polymers in water systems, or to monitorpolymers that may be present in waste fluids before disposal, or tomonitor the polymer used in fluids for down-hole oil well applications,or to monitor polymers that may be present in fluids used to wash amanufactured product.

[0004] As seen from the above list of possible applications of polymermonitoring, the purpose of such monitoring may be to trace or track ordetermine the level of the polymer itself, or to trace or track ordetermine the level of some substance in association with the polymer,or to determine some property of the polymer or substance in associationwith the polymer, for instance its leachability.

[0005] There are many industrial water systems. Because water resourcesare becoming limited and efficient utilization of water is required,various methods have been adopted to reduce the amount of water used inall industrial water systems. As the methods for reducing the amount ofwater are put into practice, unfavorable events can occur. Theseunfavorable events occur because the quality of the water in the systemis progressively deteriorated. These unfavorable events can include theformation of scale.

[0006] To prevent or minimize unfavorable events, various kinds oftreatment agents for treatment of water systems have been used. It hasbeen found that organic substances, including certain types of treatmentpolymers, are effective for preventing formation of scale. These certaintypes of treatment polymers are known to persons of ordinary skill inthe art of industrial water treatment and are widely used by themselvesor as one of many possible components in scale inhibition products.

[0007] When a treatment polymer is used for preventing formation ofscale the concentration of the treatment polymer in the water system isthe important factor so that the treatment polymer performs the desiredfunction with good efficiency. For example, a treatment polymer added toa cooling water system can be consumed by many causes. With consumption,the amount of the treatment polymer dissolved in the cooling water doesnot remain the same as the amount added to the cooling water. Therefore,it is important for the optimum operation of an industrial water systemthat practical methods are known to determine the concentration oftreatment polymers in the water of the industrial water system.

[0008] In general practice, the amount of the treatment polymer added tothe water in an industrial water system can be measured using variousanalytical methods. The use of an inert fluorescent tracer or massbalance measurement method as described in U.S. Pat. Nos. 4,783,314;4,992,380; and 5,171,450, hereby incorporated by reference; to performthis analysis is known in the art.

[0009] In the inert fluorescent tracer method, an inert fluorescenttracer is added to an industrial water system, with the amount of inertfluorescent tracer added being proportional to the amount of thetreatment polymer added. By using a fluorometer to measure thefluorescent signal of the inert fluorescent tracer, the amount of theinert fluorescent tracer can be determined by using a calibration curveto relate the amount of fluorescent signal detected to the amount of theinert fluorescent tracer present. Because the inert fluorescent tracerand the treatment polymer are added to the industrial water system inknown proportions, by knowing the amount of inert fluorescent tracerpresent it also means that the amount of treatment polymer present isknown.

[0010] The inert fluorescent tracer method can be conducted on-line andin real time so that any changes in the amount of treatment polymerbeing added to the system can be made immediately.

[0011] As a complement to the use of an inert tracer system, it has beenfound that treatment polymers that are used as components of scaleinhibitors in industrial water systems could be monitored if tagged witha fluorescent monomer. The amount of fluorescent monomer incorporatedinto the tagged treatment polymer must be enough so that thefluorescence of the tagged treatment polymer can be adequately measured;however, it must not be so much that the performance of the taggedtreatment polymer as a treatment agent for the water is decreased.Because the concentration of the tagged treatment polymer itself can bedetermined using a fluorometer, it is now possible to measureconsumption of the tagged treatment polymer directly. It is important tobe able to measure consumption directly because consumption of atreatment polymer usually indicates that a non-desired event, such asscaling, is occurring. Thus, by being able to measure consumption of thetagged treatment polymer, there can be achieved an on-line, real time,in-situ measurement of scaling activity in the cooling system.

[0012] Certain tagged treatment polymers are known, see U.S. Pat. No.5,986,030, and U.S. patent application Ser. 09/465,146, filed Dec. 16,1999, now pending, hereby incorporated by reference. However, there isnot an abundance of viable tagged treatment polymers for use astreatment polymers in industrial water systems. Therefore, it isdesirable to produce additional tagged treatment polymers that have afluorescent signal so that a fluorometer can be used to measure thefluorescent signal of the tagged treatment polymer and determine theconcentration of tagged treatment polymer currently present in theindustrial water system from that information.

[0013] It is known that tagging of polymers is difficult to accomplishbecause of the difficulty in chemically combining fluorescent moietieswith non-fluorescent polymers. Therefore, in order to synthesize taggedtreatment polymers it is also desirable to produce fluorescent monomersthat are readily polymerized to form tagged treatment polymers.

SUMMARY OF THE INVENTION

[0014] The first aspect of the instant claimed invention is afluorescent monomer selected from the group consisting of compounds ofthe formulae:

[0015] wherein R₃ is sulfonic acid and its salts or carboxylic acid andits salts or allyloxy or vinylbenzyloxy; and R₄ is sulfonic acid and itssalts or carboxylic acid and its salts or allyloxy or vinylbenzyloxy;with the proviso that when one of R₃ or R₄ is sulfonic acid and itssalts or carboxylic acid and its salts, the other must be allyloxy orvinylbenzyloxy.

[0016] The second aspect of the instant claimed invention is a taggedtreatment polymer selected from the group consisting of:

(1) G_(a)Q_(j)W_(t)

[0017] wherein G is Monomer (Purple), as previously defined;

[0018] wherein Q is selected from the group consisting of acrylic acidand salts thereof, methacrylic acid and salts thereof, maleic acid andsalts thereof, maleic anhydride, acrylamide, crotonic acid,acrylamidomethylpropane sulfonic acid and salts thereof;

[0019] wherein W is selected from the group consisting of:

[0020] acrylic acid and salts thereof, methacrylic acid and saltsthereof, itaconic acid and salts thereof, maleic acid and salts thereof,maleic anhydride, crotonic acid and salts thereof, acrylamide,methacrylamide, vinyl sulfonic acid, styrene sulfonate,N-tertbutylacrylamide, N-isopropylacrylamide, butoxymethylacrylamide,N,N-dimethylacrylamide, N,N-diethylacrylamide, dimethylaminoethylacrylate methyl chloride quaternary salts, dimethylaminoethyl acrylatebenzyl chloride quaternary salts, dimethylaminoethyl acrylate methylsulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfatequaternary salt, dimethylaminoethyl acrylamide methyl sulfate quaternarysalts, dimethylaminopropyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl methacrylamide methyl sulfate quaternary salts,diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylaminoethyl methacrylate acid salts (including, but not limited to, sulfuricacid and hydrochloride acid salts), dimethylaminoethyl methacrylatemethyl chloride quaternary salt, dimethylaminoethyl methacrylate benzylchloride quaternary salt, methacrylamidopropyl trimethyl ammoniumchloride, acrylamidopropyl trimethyl ammonium chloride, methylene bisacrylamide, triallylamine, acid salts of triallylamine, ethylene glycoldimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate,hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycoldimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycoldimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonicacid and the sodium salt thereof, vinyl alcohol, vinyl acetate, andN-vinylpyrrolidone;

[0021] with the proviso that Q and W cannot both be the same;

[0022] wherein a is from about 0.001 to about 10.0 mole percent;

[0023] wherein j is from about 0 to about 99.999 mole percent;

[0024] wherein t is from about 0 to about 99.999 mole percent; and

[0025] wherein a+j+t=100;

(2) G_(a)Q_(v)W_(f)S_(c)

[0026] wherein G is as previously defined;

[0027] wherein Q is as previously defined;

[0028] wherein W is as previously defined, with the proviso that Q and Wcannot both be the same;

[0029] wherein S is selected from the group consisting ofsulfomethylacrylamide and sulfoethylacrylamide;

[0030] wherein a is from about 0.001 to about 10.00 mole percent;

[0031] wherein v is from about 0 to about 97.999 mole percent;

[0032] wherein f is from about 1 to about 97.999 mole percent;

[0033] wherein c is from about 1 to about 40 mole percent; and

[0034] wherein a+v+f+c=100.

[0035] The third aspect of the instant claimed invention is a processfor the inhibition of scale formation in an industrial water systemwhich comprises introducing into said industrial water system a taggedtreatment polymer selected from the group consisting of:

(1) G_(a)Q_(j)W_(t)

[0036] wherein G is Monomer (Purple), as previously defined;

[0037] wherein Q is selected from the group consisting of acrylic acidand salts thereof, methacrylic acid and salts thereof, maleic acid andsalts thereof, maleic anhydride, acrylamide, crotonic acid,acrylamidomethylpropane sulfonic acid and salts thereof;

[0038] wherein W is selected from the group consisting of:

[0039] acrylic acid and salts thereof, methacrylic acid and saltsthereof, itaconic acid and salts thereof, maleic acid and salts thereof,maleic anhydride, crotonic acid and salts thereof, acrylamide,methacrylamide, vinyl sulfonic acid, styrene sulfonate,N-tertbutylacrylamide, N-isopropylacrylamide, butoxymethylacrylamide,N,N-dimethylacrylamide, N,N-diethylacrylamide, dimethylaminoethylacrylate methyl chloride quaternary salts, dimethylaminoethyl acrylatebenzyl chloride quaternary salts, dimethylaminoethyl acrylate methylsulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfatequaternary salt, dimethylaminoethyl acrylamide methyl sulfate quaternarysalts, dimethylaminopropyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl methacrylamide methyl sulfate quaternary salts,diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylaminoethyl methacrylate acid salts (including, but not limited to, sulfuricacid and hydrochloride acid salts), dimethylaminoethyl methacrylatemethyl chloride quaternary salt, dimethylaminoethyl methacrylate benzylchloride quaternary salt, methacrylamidopropyl trimethyl ammoniumchloride, acrylamidopropyl trimethyl ammonium chloride, methylene bisacrylamide, triallylamine, acid salts of triallylamine, ethylene glycoldimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate,hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycoldimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycoldimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonicacid and the sodium salt thereof, vinyl alcohol, vinyl acetate, andN-vinylpyrrolidone;

[0040] with the proviso that Q and W cannot both be the same;

[0041] wherein a is from about 0.001 to about 10.0 mole percent;

[0042] wherein j is from about 0 to about 99.999 mole percent;

[0043] wherein t is from about 0 to about 99.999 mole percent; and

[0044] wherein a+j+t=100;

(2) G_(a)Q_(v)W_(f)S_(c)

[0045] wherein G is as previously defined;

[0046] wherein Q is as previously defined;

[0047] wherein W is as previously defined, with the proviso that Q and Wcannot both be the same;

[0048] wherein S is selected from the group consisting ofsulfomethylacrylamide and sulfoethylacrylamide;

[0049] wherein a is from about 0.001 to about 10.00 mole percent;

[0050] wherein v is from about 0 to about 97.999 mole percent;

[0051] wherein f is from about 1 to about 97.999 mole percent;

[0052] wherein c is from about 1 to about 40 mole percent; and

[0053] wherein a+v+f+c=100.

[0054] in an amount sufficient to inhibit scale formation.

[0055] The fourth aspect of the instant claimed invention is a methodfor maintaining the desired amount of tagged treatment polymer in anindustrial water system comprising the steps of:

[0056] i) adding to said industrial water system a tagged treatmentpolymer, selected from the group consisting of:

(1) G_(a)Q_(j)W_(t)

[0057] wherein G is Monomer (Purple), as previously defined;

[0058] wherein Q is selected from the group consisting of acrylic acidand salts thereof, methacrylic acid and salts thereof, maleic acid andsalts thereof, maleic anhydride, acrylamide, crotonic acid,acrylamidomethylpropane sulfonic acid and salts thereof;

[0059] wherein W is selected from the group consisting of:

[0060] acrylic acid and salts thereof, methacrylic acid and saltsthereof, itaconic acid and salts thereof, maleic acid and salts thereof,maleic anhydride, crotonic acid and salts thereof, acrylamide,methacrylamide, vinyl sulfonic acid, styrene sulfonate,N-tertbutylacrylamide, N-isopropylacrylamide, butoxymethylacrylamide,N,N-dimethylacrylamide, N,N-diethylacrylamide, dimethylaminoethylacrylate methyl chloride quaternary salts, dimethylaminoethyl acrylatebenzyl chloride quaternary salts, dimethylaminoethyl acrylate methylsulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfatequaternary salt, dimethylaminoethyl acrylamide methyl sulfate quaternarysalts, dimethylaminopropyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl methacrylamide methyl sulfate quaternary salts,diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylaminoethyl methacrylate acid salts (including, but not limited to, sulfuricacid and hydrochloride acid salts), dimethylaminoethyl methacrylatemethyl chloride quaternary salt, dimethylaminoethyl methacrylate benzylchloride quaternary salt, methacrylamidopropyl trimethyl ammoniumchloride, acrylamidopropyl trimethyl ammonium chloride, methylene bisacrylamide, triallylamine, acid salts of triallylamine, ethylene glycoldimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate,hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycoldimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycoldimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonicacid and the sodium salt thereof, vinyl alcohol, vinyl acetate, andN-vinylpyrrolidone;

[0061] with the proviso that Q and W cannot both be the same;

[0062] wherein a is from about 0.001 to about 10.0 mole percent;

[0063] wherein j is from about 0 to about 99.999 mole percent;

[0064] wherein t is from about 0 to about 99.999 mole percent; and

[0065] wherein a+j+t=100;

(2) G_(a)Q_(v)W_(f)S_(c)

[0066] wherein G is as previously defined;

[0067] wherein Q is as previously defined;

[0068] wherein W is as previously defined, with the proviso that Q and Wcannot both be the same;

[0069] wherein S is selected from the group consisting ofsulfomethylacrylamide and sulfoethylacrylamide;

[0070] wherein a is from about 0.001 to about 10.00 mole percent;

[0071] wherein v is from about 0 to about 97.999 mole percent;

[0072] wherein f is from about 1 to about 97.999 mole percent;

[0073] wherein c is from about 1 to about 40 mole percent; and

[0074] wherein a+v+f+c=100.

[0075] ii) using a fluorometer to detect the fluorescent signal of saidtagged treatment polymer;

[0076] iii) converting the fluorescent signal of said tagged treatmentpolymer to the concentration of said tagged treatment polymer; and

[0077] iv) adjusting the concentration of said tagged treatment polymeraccording to what the desired concentration is for said tagged treatmentpolymer in said industrial water system.

[0078] The fifth aspect of the instant claimed invention is a method formaintaining the desired amount of tagged treatment polymer in anindustrial water system comprising the steps of:

[0079] a) adding an inert tracer and a tagged treatment polymer to thewater of an industrial water system, wherein said tagged treatmentpolymer is selected from the group consisting of:

(1) G_(a)Q_(j)W_(t)

[0080] wherein G is Monomer (Purple), as previously defined;

[0081] wherein Q is selected from the group consisting of acrylic acidand salts thereof, methacrylic acid and salts thereof, maleic acid andsalts thereof, maleic anhydride, acrylamide, crotonic acid,acrylamidomethylpropane sulfonic acid and salts thereof;

[0082] wherein W is selected from the group consisting of:

[0083] acrylic acid and salts thereof, methacrylic acid and saltsthereof, itaconic acid and salts thereof, maleic acid and salts thereof,maleic anhydride, crotonic acid and salts thereof, acrylamide,methacrylamide, vinyl sulfonic acid, styrene sulfonate,N-tertbutylacrylamide, N-isopropylacrylamide, butoxymethylacrylamide,N,N-dimethylacrylamide, N,N-diethylacrylamide, dimethylaminoethylacrylate methyl chloride quaternary salts, dimethylaminoethyl acrylatebenzyl chloride quaternary salts, dimethylaminoethyl acrylate methylsulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfatequaternary salt, dimethylaminoethyl acrylamide methyl sulfate quaternarysalts, dimethylaminopropyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl methacrylamide methyl sulfate quaternary salts,diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylaminoethyl methacrylate acid salts (including, but not limited to, sulfuricacid and hydrochloride acid salts), dimethylaminoethyl methacrylatemethyl chloride quaternary salt, dimethylaminoethyl methacrylate benzylchloride quaternary salt, methacrylamidopropyl trimethyl ammoniumchloride, acrylamidopropyl trimethyl ammonium chloride, methylene bisacrylamide, triallylamine, acid salts of triallylamine, ethylene glycoldimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate,hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycoldimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycoldimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonicacid and the sodium salt thereof, vinyl alcohol, vinyl acetate, andN-vinylpyrrolidone;

[0084] with the proviso that Q and W cannot both be the same;

[0085] wherein a is from about 0.001 to about 10.0 mole percent;

[0086] wherein j is from about 0 to about 99.999 mole percent;

[0087] wherein t is from about 0 to about 99.999 mole percent; and

[0088] wherein a+j+t=100;

(2) G_(a)Q_(v)W_(f)S_(c)

[0089] wherein G is as previously defined;

[0090] wherein Q is as previously defined;

[0091] wherein W is as previously defined, with the proviso that Q and Wcannot both be the same;

[0092] wherein S is selected from the group consisting ofsulfomethylacrylamide and sulfoethylacrylamide;

[0093] wherein a is from about 0.001 to about 10.00 mole percent;

[0094] wherein v is from about 0 to about 97.999 mole percent;

[0095] wherein f is from about 1 to about 97.999 mole percent;

[0096] wherein c is from about 1 to about 40 mole percent; and

[0097] wherein a+v+f+c=100.

[0098] such that a desired concentration of said tagged treatmentpolymer is present in said water;

[0099] b) using a fluorometer to detect the fluorescent signals of saidinert tracer and said tagged treatment polymer;

[0100] c) converting the fluorescent signals of said inert tracer andsaid tagged treatment polymer to the concentration of said inert tracerand said tagged treatment polymer; and

[0101] d) adjusting the concentration of said tagged treatment polymeraccording to what the desired concentration is for said tagged treatmentpolymer in said industrial water system.

DETAILED DESCRIPTION OF THE INVENTION

[0102] Throughout this patent application the following definitionsapply:

[0103] “anionic counter ion” refers to an organic or inorganic ion thatbears a negative charge to counterbalance the positive charge present onthe monomer. Examples include, but are not limited to chloride, sulfate,acetate, methylsulfate, hydroxide and bromide;

[0104] “aliphatic amine” refers to amines in which the amine group isattached to a saturated carbon atom;

[0105] “substituted aliphatic amine” refers to amines in which the aminegroup is attached to a saturated carbon of an organic molecule which maybear functional groups such as hydroxyl, carboxyl, etc.;

[0106] “1,2-diamino-substituted aromatic compound” refers to aromaticdiamines in which the two amino groups are attached to two adjacentcarbons of an aromatic compound;

[0107] “diamines” refers to an organic molecule which bears two aminogroups anywhere in the molecule;

[0108] “Aldrich” refers to Aldrich Chemical Company, P.O. Box 2060,Milwaukee, Wis. 53201 USA, Telephone Numbers (414) 273-3850 and (800)558-9160;

[0109] “alkyl”, whenever it is used, refers to a fully saturatedhydrocarbon moiety with from 1 to 10 carbon atoms;

[0110] “dialkylamino” refers to a moiety of the formula R₂₁—N—R₂₂, whereR₂₁ and R₂₂ are alkyl;

[0111] “alkoxy” refers to a moiety of the formula RO—, where R is alkyl;

[0112] “alkylamidoalkyl” refers to a moiety of the formula R—C(O)NH—R₁—,where R and R₁ are alkyl;

[0113] “alkylamino” refers to a moiety of the formula R—NH—, where R isalkyl;

[0114] “alkoxylalkyl” refers to a moiety of the formula R—O—R₁, where Rand R₁ are alkyl;

[0115] “aryl” refers to a moiety of the formula Ar—, where Ar is anaromatic unit; “carboxylate” refers to a moiety of —C(O)OM, where M isH, Na or another cationic counter ion;

[0116] “halogen” refers to a moiety selected from the group consistingof F, Cl, Br, and I;

[0117] “hydroxyalkyl” refers to a moiety where an —OH group is attachedto an alkyl group;

[0118] “Nalco” refers to Ondeo Nalco Company, Ondeo Nalco Center,Naperville, Ill. (630) 305-1000;

[0119] “vinyl” refers to a moiety which has a carbon-carbon double bond;

[0120] “vinylbenzyl” refers to a moiety of the formula;

[0121] and “vinylbenzyloxy” refers to a moiety of the formula:

[0122] “Chain Transfer Agent” refers to any molecule, used infree-radical polymerization, which will react with a polymer radicalforming a dead polymer and a new radical. Representative Chain TransferAgents are listed by K. C. Berger and G. Brandrup, “Transfer Constantsto Monomer, Polymer, Catalyst, Solvent, and Additive in Free RadicalPolymerization,” Section II, pp. 81-151, in “Polymer Handbook,” editedby J. Brandrup and E. H. Immergut, 3d edition, 1989, John Wiley & Sons,New York.

[0123] “Cross-Linking Agent” refers to an ethylenically unsaturatedmonomer either containing at least two sites of ethylenic unsaturationor containing one site of ethylenic unsaturation and one site of areactive group such as an epoxide or an aldehyde. A Cross-Linking Agentis added to branch or increase the molecular weight of the taggedtreatment polymer of this invention. Representative Cross-Linking Agentsinclude N,N-methylenebisacrylamide, N,N-methylenebismethacrylamide,polyethylene glycol diacrylate, ethylene glycol dimethacrylate,diethylene glycol dimethacrylate, triethylene glycol dimethacrylate,polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate,N-vinyl acrylamide, divinyl benzene, triallyl ammonium salts, N-methylallylacrylamide, glycidyl acrylate, acrolein, methylolacrylamide,glyoxal, epichlorohydrin, and the like. The crosslinker is added at fromabout 0.0001 to about 10, preferably from about 0.0001 to about 0.2weight percent based on the weight of the polymer;

[0124] “Branching Agent” refers to a “Cross-Linking Agent” that isadministered at a low level (less than 0.05 weight percent based on theweight of the polymer). It is understood that Branching Agents are addedto form “branches” not cross-links; and

[0125] “HLB” refers to a hydrophilic-lipophilic balance number.

[0126] The present invention is based upon the discovery of a group offluorescent monomers which are useful in the preparation of taggedtreatment polymers containing same, with said tagged treatment polymersin turn being able to provide a means for achieving better monitoring inindustrial water systems.

[0127] The first aspect of the instant claimed invention is afluorescent monomer selected from the group consisting of compounds ofthe formulae:

[0128] wherein R₃ is sulfonic acid and its salts or carboxylic acid andits salts or allyloxy or vinylbenzyloxy; and

[0129] R₄ is sulfonic acid and its salts or carboxylic acid and itssalts or allyloxy or vinylbenzyloxy; with the proviso that when one ofR₃ or R₄ is sulfonic acid and its salts or carboxylic acid and itssalts, the other must be allyloxy or vinylbenzyloxy.

[0130] Preferred monomers are selected from the group consisting of

[0131] Monomer (Purple),

[0132] wherein R₃ is sulfonic and carboxylic acid; and

[0133] R₄ allyloxy and vinylbenzyloxy.

[0134] The most preferred monomers are monomers of formula Monomer(Purple) where

[0135] R₃ is carboxylic acid; and

[0136] R₄ is vinylbenzyloxy and allyloxy.

[0137] Acceptable names for the most preferred monomers are:

[0138] 5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′ benzimidazole and

[0139] 6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole.

[0140] Monomers of formula (Purple) can be synthesized by using twodifferent synthetic routes. Materials required for these syntheses arecommercially available and can be obtained from Aldrich.

[0141] The first synthetic route involves initially reacting a sulfonicor carboxylic-substituted naphthalic anhydride with 2,3-diamino-phenol.This compound is then further reacted with an allyl or vinylbenzylhalide to yield Monomer (Purple) where R₃ is allyloxy or vinylbenzyloxyand R₄ is carboxylic or sulfonic acid.

[0142] The second synthetic route involves reacting4-hydroxy-1,8-naphthalic anhydride with a carboxylic orsulfonic-substituted-diamino aromatic compound. This compound is thenfurther reacted with an allyl or vinylbenzyl halide to yield Monomer(Purple) where R₃ is carboxylic or sulfonic acid and R₄ is allyloxy orvinylbenzyloxy.

[0143] “Tagging” the polymer through the use of the fluorescent monomersof this invention is achieved by synthesizing the polymer in thepresence of the fluorescent monomer.

[0144] Accordingly, once a monomer of Monomer (Purple) is synthesized,the selected monomer can be used to synthesize tagged treatment polymersof formula:

(1) G_(a)Q_(j)W_(t)

[0145] wherein G is Monomer (Purple), as previously defined;

[0146] wherein Q is selected from the group consisting of acrylic acidand salts thereof, methacrylic acid and salts thereof, maleic acid andsalts thereof, maleic anhydride, acrylamide, crotonic acidacrylamidomethylpropane sulfonic acid and salts thereof;

[0147] wherein W is selected from the group consisting of:

[0148] acrylic acid and salts thereof, methacrylic acid and saltsthereof, itaconic acid and salts thereof, maleic acid and salts thereof,maleic anhydride, crotonic acid and salts thereof, acrylamide,methacrylamide, vinyl sulfonic acid, styrene sulfonate,N-tertbutylacrylamide, N-isopropylacrylamide, butoxymethylacrylamide,N,N-dimethylacrylamide, N,N-diethylacrylamide, dimethylaminoethylacrylate methyl chloride quaternary salts, dimethylaminoethyl acrylatebenzyl chloride quaternary salts, dimethylaminoethyl acrylate methylsulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfatequaternary salt, dimethylaminoethyl acrylamide methyl sulfate quaternarysalts, dimethylaminopropyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl methacrylamide methyl sulfate quaternary salts,diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylaminoethyl methacrylate acid salts (including, but not limited to, sulfuricacid and hydrochloride acid salts), dimethylaminoethyl methacrylatemethyl chloride quaternary salt, dimethylaminoethyl methacrylate benzylchloride quaternary salt, methacrylamidopropyl trimethyl ammoniumchloride, acrylamidopropyl trimethyl ammonium chloride, methylene bisacrylamide, triallylamine, acid salts of triallylamine, ethylene glycoldimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate,hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycoldimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycoldimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonicacid and the sodium salt thereof, vinyl alcohol, vinyl acetate, andN-vinylpyrrolidone;

[0149] with the proviso that Q and W cannot both be the same;

[0150] wherein a is from about 0.001 to about 10.0 mole percent;

[0151] wherein j is from about 0 to about 99.999 mole percent;

[0152] wherein t is from about 0 to about 99.999 mole percent; and

[0153] wherein a+j+t=100;

(2) G_(a)Q_(v)W_(f)S_(c)

[0154] wherein G is as previously defined;

[0155] wherein Q is as previously defined;

[0156] wherein W is as previously defined, with the proviso that Q and Wcannot both be the same;

[0157] wherein S is selected from the group consisting ofsulfomethylacrylamide and sulfoethylacrylamide;

[0158] wherein a is from about 0.001 to about 10.00 mole percent;

[0159] wherein v is from about 0 to about 97.999 mole percent;

[0160] wherein f is from about 1 to about 97.999 mole percent;

[0161] wherein c is from about 1 to about 40 mole percent; and

[0162] wherein a+v+f+c=100.

[0163] These tagged treatment polymers can be synthesized by followingthe procedure for conventional free radical polymerization in an aqueousmedium. They can be made by water-in-oil polymerization methods ordispersion polymerization methods or solution polymerization methods.For those tagged treatment polymers containing a sulfomethylated orsulfoethylated acrylamide, the polymers are first created with anacrylamide moiety, and then the acrylamide groups are sulfomethylatedusing a suitable “sulfo” reagent such as formaldehyde and sodiummetabisulfite.

Procedure for Synthesizing Water-In-Oil Emulsion Polymers

[0164] The preparation of high molecular weight water-in-oil emulsionpolymers has been described in the following references: U.S. Pat. No.2,982,749 assigned to The Dow Chemical Company; U.S. Pat. No. 3,284,393assigned to The Dow Chemical Company; U.S. Pat. No. 3,734,873 assignedto Nalco Chemical Company; “Mechanism, Kinetics and Modeling of theInverse-Microsuspension Homopolymerization of Acrylamide,” by Hundeler,D., Hamielec, A. and Baade, W., Polymer (1989), 30(1), 127-42; and“Mechanism, Kinetics and Modeling of Inverse-MicrosuspensionPolymerization: 2. Copolymerization of Acrylamide with QuaternaryAmmonium Cationic Monomers,” by D. Hunkeler and A. E. Hamielec; Polymer(1991), 32(14), 2626-40.

[0165] A general procedure for the manufacture of water-in-oil emulsiontagged treatment polymers is provided to illustrate the preparation ofthese tagged treatment polymers using fluorescent monomers. The typesand quantities of specific components in the formula (monomers,initiators, Chain Transfer Agents, for example) will vary depending uponthe type of polymer (cationic, anionic, nonionic) that is beingsynthesized.

[0166] An aqueous phase is prepared by mixing together in water one ormore water soluble monomers, and different polymerization additives suchas inorganic salts, chelants, pH buffers, Chain Transfer Agents andBranching or Cross-Linking Agents. In order to synthesize the taggedtreatment polymers of the instant claimed invention, a monomer offormula Monomer (Purple) is included in the aqueous phase at the desiredlevel.

[0167] An organic phase is prepared by mixing together an inerthydrocarbon liquid with one or more oil soluble surfactants. Thesurfactant mixture should have a low HLB, to ensure the formation of anoil continuous emulsion. Appropriate surfactants for water-in-oilemulsion polymerizations, which are commercially available, are compiledin the North American Edition of McCutcheon's Emulsifiers & Detergents.The oil phase may need to be heated to ensure the formation of ahomogeneous oil solution.

[0168] The oil phase is charged into a reactor equipped with a mixer, athermocouple, a nitrogen purge tube, and a condenser. Adding the aqueousphase to the reactor containing the oil phase with vigorous stirringforms an emulsion. The resulting emulsion is heated to the desiredtemperature, purged with nitrogen, and a free-radical initiator isadded. The reaction mixture is stirred for several hours under anitrogen atmosphere at the desired temperature. Upon completion of thereaction, the water-in-oil emulsion polymer is cooled to roomtemperature, where any desired post-polymerization additives, such asantioxidants, or a high HLB surfactant (as described in U.S. Pat. No.3,734,873) may be added.

[0169] The resulting emulsion polymer is a free-flowing liquid. Anaqueous solution of the water-in-oil emulsion polymer can be generatedby adding a desired amount of the emulsion polymer to water withvigorous mixing in the presence of a high-HLB surfactant (as describedin U.S. Pat. No. 3,734,873).

Procedure for Synthesizing Dispersion Polymers

[0170] The preparation of dispersion polymers has been described in thefollowing references: U.S. Pat. No. 4,929,655, assigned to HymoCorporation; U.S. Pat. No. 5,006,590, assigned to Hymo Corporation; U.S.Pat. No. 5,597,859, assigned to Nalco Chemical Company; European Patent657,478; U.S. Pat. No. 5,597,858, assigned to Nalco Chemical Company andEuropean Patent 630,909.

[0171] A general procedure for the manufacture of dispersion taggedtreatment polymers is provided in the following text in order toillustrate the preparation of dispersion tagged treatment polymerscomprising the fluorescent monomers described herein. The types andquantities of specific components in the formula (salts and stabilizerpolymers, for example) will vary depending upon the type of polymer(cationic, anionic, nonionic) that is being synthesized.

[0172] An aqueous solution containing one or more inorganic salts, oneor more water-soluble monomers, any polymerization additives such aschelants, pH buffers, Chain Transfer Agents, Branching or Cross-LinkingAgents and a water-soluble stabilizer polymer is charged to a reactorequipped with a mixer, a thermocouple, a nitrogen purging tube, and awater condenser. The monomer solution is mixed vigorously, heated to thedesired temperature, and then a water-soluble initiator is added. Thesolution is purged with nitrogen while maintaining temperature andmixing for several hours. After this time, the products are cooled toroom temperature, and any post-polymerization additives are charged tothe reactor. Water continuous dispersions of water-soluble polymers arefree flowing liquids with product viscosities generally 100-10,000 cP,measured at low shear. Thus, in order to prepare tagged polymers asdispersions, a monomer of formula Monomer (Purple) is included in thereaction mixture at the desired level.

Procedure for Synthesizing Solution Polymers

[0173] A general procedure for the manufacture of solution polymers isprovided to illustrate the preparation of the solution tagged treatmentpolymers comprising the fluorescent monomers described herein. Onetypical process is described as follows: One or more monomers are addedto a vessel followed by neutralization with a suitable base. Thefluorescent monomer can then be added to this monomer solution afterneutralization or alternatively, to the reaction vessel. A determinedamount of water is then added to the reaction vessel, which is thenheated and purged. Polymerization catalysts may also be added to thevessel initially or fed in gradually during the course of the reaction.Water soluble polymerization initiators such as any azo or redoxinitiator or combination thereof are added along with the monomersolution to the reaction mixture in separate feeds over the same amountof time, usually 2 to 6 hours. The reaction temperature is maintained atabout 60-70° C. Additional initiator may be used after addition iscomplete to reduce residual monomer levels.

[0174] The amount of fluorescent monomer that is used should be anamount sufficient to allow the tagged treatment polymer to be detectedin the aqueous environment that it is used. The minimum amount offluorescent moiety that can be used is that amount which gives asignal-to-noise ratio (S/N) of 3 at the desired tagged treatment polymerdosage. The signal-to-noise ratio is that value where the magnitude ofthe transduced signal (including but not limited to electronic andoptical signals) due to the presence of a target analytic in ameasurement device is greater than or equal to a level three (3) timesthe magnitude of a transduced signal where the analyte (species) ofinterest is not present in the measurement device.

[0175] The amount of fluorescent monomer in the tagged treatmentpolymers is in the range of from about 0.001 mole percent to about 10mole percent, preferably from about 0.01 mole percent to about 0.4 molepercent, and most preferably from about 0.05 mole percent to about 0.35mole percent. For purposes of this patent application, mole percent ofall monomers in the tagged treatment polymer is calculated based onweight percent. For purposes of this patent application, the subscriptsa, j, t, v, f and c refer to the mole percent of each monomer componentof the tagged treatment polymers.

[0176] The remainder of the tagged treatment polymer can have one, twoor three additional monomers in it.

[0177] All molecular weights in this patent application are weightaverage molecular weights measured by gel permeation chromatography(GPC) calculated from both refractive index and fluorescent detectortraces using polystyrene sulfonate (PSS) molecular weight standards.Tagged treatment polymers that have a wide range of molecular weightscan be prepared by using the procedures described previously by thoseskilled in the art.

[0178] The molecular weights of the instant claimed tagged treatmentpolymers are from about 500 atomic mass units (hereinafter “a.m.u.”) toabout 10,000,000 a.m.u. Preferably the molecular weights are from about2000 a.m.u. to about 500,000 a.m.u. Most preferably, the molecularweights are from about 5000 a.m.u. to about 40,000 a.m.u.

[0179] Preferred tagged polymers are made via solution polymerizationtechniques and have a molecular weight from about 5,000 a.m.u. to about40,000 a.m.u.

[0180] Preferred tagged treatment polymers are where said fluorescentmonomer is selected from the group consisting of:

[0181] 5-allyloxy-4′-carboxy-1,8 naphthoylene-1′,2′-benzimidazole(5ACNB) and6-vinylbenzyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′-benzimidazole(6-VBCNB).

[0182] The more preferred polymers are where G is Monomer (Purple) aspreviously defined; Q, if present in the polymer, is selected from thegroup consisting of acrylamide and acrylic acid;

[0183] W, if present in the polymer, is selected from the groupconsisting of acrylamide and acrylamidomethylpropane sulfonic acid; and

[0184] S, if present in the polymer, is N-sulfomethylacrylamide.

[0185] The most preferred polymers are selected from the groupconsisting of

[0186] 0.04 mole % 5-ACNB, 49.98 mole % acrylic acid, 49.98 mole %acrylamide; and

[0187] 0.04 mole % 6-VBCNB, 49.98 mole % acrylic acid, 49.98 mole %acrylamide.

[0188] Once created the tagged treatment polymers of the instant claimedinvention can be used as scale inhibitors in industrial water systems.As these polymers are consumed performing that function, theirfluorescent signal will decrease and thus the decrease in thefluorescent signal can be used to indicate that undesired scaling istaking place.

[0189] The tagged treatment polymers containing a fluorescent monomercan be used in industrial water systems. Examples of industrial watersystems are cooling tower water systems (including open recirculating,closed and once-through systems); petroleum wells, downhole formations,geothermal wells and other oil field applications; boilers and boilerwater systems; mineral process waters including mineral washing,flotation and benefaction; paper mill digesters, paper production,washers, bleach plants and white water systems; black liquor evaporatorsin the pulp industry; gas scrubbers and air washers; continuous castingprocesses in the metallurgical industry; air conditioning andrefrigeration systems; industrial and petroleum process water; indirectcontact cooling and heating water, such as pasteurization water; waterreclamation and purification systems; membrane filtration water systems;food processing streams (meat, vegetable, sugar beets, sugar cane,grain, poultry, fruit and soybean); and waste treatment systems as wellas in clarifiers, liquid-solid applications, municipal sewage treatmentand industrial or municipal water systems.

[0190] The tagged treatment polymer comprising a fluorescent monomer maybe used in the industrial water systems singly or in combination withother polymers, which are not tagged. The dosage rate of taggedtreatment polymer in an industrial water system, when it is being usedas a scale inhibitor, is from about 1 to about 100 milligrams of solidcomponent active per liter of water.

[0191] The third aspect of the instant claimed invention is a processfor the inhibition of scale formation in an industrial water systemwhich comprises introducing into said industrial water system a taggedtreatment polymer, previously described, in an amount sufficient toinhibit scale formation. The amount of the tagged treatment polymercomprising the fluorescent monomer added to an industrial water systemis in the range of about 1.0 milligrams (mg) to about 30 milligrams ofthe total solid polymer actives per liter of water in the system. Thisis equivalent to about 1 part per million (ppm) to about 30 ppm.

[0192] When used in an industrial water system, the fluorescent signalof the tagged treatment polymers can be used to determine how muchtagged treatment polymer is present in the industrial water system.Therefore, the fourth aspect of the instant claimed invention is:

[0193] A method for maintaining the desired amount of tagged treatmentpolymer in an industrial water system comprising the steps of:

[0194] i) adding to said industrial water system a tagged treatmentpolymer, wherein said tagged treatment polymer is as previouslydescribed;

[0195] ii) using a fluorometer to detect the fluorescent signal of saidtagged treatment polymer;

[0196] iii) converting the fluorescent signal of said tagged treatmentpolymer to the concentration of said tagged treatment polymer; and

[0197] iv) adjusting the concentration of said tagged treatment polymeraccording to what the desired concentration is for said tagged treatmentpolymer in said industrial water system.

[0198] The fifth aspect of the instant claimed invention is as follows.

[0199] A method for maintaining the desired amount of tagged treatmentpolymer in an industrial water system comprising the steps of:

[0200] a) adding an inert tracer and a tagged treatment polymer, aspreviously described, to water such that a desired concentration of saidtagged treatment polymer is present in said water;

[0201] b) using a fluorometer to detect the fluorescent signals of saidinert tracer and said tagged treatment polymer;

[0202] c) converting the fluorescent signals of said inert tracer andsaid tagged treatment polymer to the concentration of said inert tracerand said tagged treatment polymer; and

[0203] d) adjusting the concentration of said tagged treatment polymeraccording to what the desired concentration is for said tagged treatmentpolymer in the industrial water system.

[0204] An advantage of the fluorescent monomers of this invention isthat in their use in the formation of a tagged treatment polymer, thefluorescent monomer is not significantly affected by other structures inthe polymer or by other ingredients in the system. Thus, the polymersare stable in the presence of STA.BR.EX®, where STA.BR,EX® is thetrademark for an oxidizing biocide, available from Nalco ChemicalCompany, One Nalco Center, Naperville, Ill. 60563.

[0205] A further advantage of the tagged treatment polymers of thisinvention is that the spectral properties, i.e. both excitation andemission of the polymers are in the near visible wavelength region (>370nm), thus allowing the use of solid state instrumentation andpotentially minimize interferences that generally occur in the UVwavelength region.

[0206] The following examples are presented to be illustrative of thepresent invention and to teach one of ordinary skill how to make and usethe invention. These examples are not intended to limit the invention orits protection in any way.

EXAMPLES Monomer Example 1

[0207]

Preparation of5-allyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole (5-ACNB)

[0208] Step One: Synthesis of5-chloro-4′-carboxy-1,8-naphthoylene-1′,2′- benzimidazole(I)

[0209] A 100 ml round bottom flask was charged with4-chloro-1,8-naphthalic anhydride (4.65 g, 19.99 mmol)3,4-diaminobenzoic acid (3.08 g, 20.24 mmol), and glacial acetic acid(50 ml). The mixture was refluxed under nitrogen for 5 hours and cooled.The solid was collected, washed with isopropanol, and dried undervacuum.

[0210] Step Two: Synthesis of5-allyloxy-4′-carboxy-1,8-naphthoylene-1′,2′- benzimidazole

[0211] A 300 ml Parr reactor was charged with5-chloro-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole(I) (0.7 g, 2.01mmol), allyl alcohol (20 ml, 0.294 mole), and potassium hydroxide (0.23g, 4.1 mmol). The reactor was purged for 10 minutes, sealed and thenheated to 150° C. for 4 hours. Upon cooling, the volatiles were strippedand a crude orange solid was obtained.

Monomer Example 2

[0212]

Preparation 6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene1′,2′-benzimidazole (6-VBCNB)

[0213] Step One: Synthesis of6-hydroxy-4′-carboxyl-1,8-naphthoylene-1′,2′-benzimidazole(I)

[0214] A 100 ml round bottom flask was charged with3-hydroxy-1,8-naphthalic anhydride (4.29 g, 20.04 mmol),3,4-diaminobenzoic acid (3.04 g, 19.97 mmol), and glacial acetic acid(50 ml). The mixture was refluxed under nitrogen for 5 hours and cooled.The solid was collected, washed with isopropanol, and dried undervacuum.

[0215] Step Two: Synthesis of6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole

[0216] A 100 ml round bottom flask was charged with6-hydroxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole(I) (1.66 g,4.5 mmol), vinyl benzyl chloride (0.92 g, 6.05 mmol), and potassiumcarbonate (2.38 g, 10 mmol). The mixture was refluxed in acetone for 8hours and cooled. The mixture was then poured into water, acidified, andthe orange solid was collected.

Polymer Example 1 Preparation of 0.04 mole % 5-ACNB/49.98 mole % AcrylicAcid/49.98 mole % Acrylamide

[0217] A reactor was charged with deionized water (125 g), and 5-ACNB(prepared according to Monomer Example 1, 0.474 g, 1.16 mmol) and heatedto 65° C. with stirring (750 rpm). At temperature, initiator solution 1(3.50 g ammonium persulfate in 19.59 g of deionized water), andinitiator solution 2 (10.48 g sodium metabisulfite in 30.30 g ofdeionized water) were added separately at a constant flow rate over aperiod of 3.25 hours. Five minutes after initiator feed had started, amonomer solution consisting of deionized water (13.57 g), acrylic acid(95.43 g, 1.33 mole), 48.7% acrylamide (193.23 g, 1.33 mole), and 50%sodium hydroxide (42.3 g, 0.529 mole) was added separately at a constantflow rate over a period of 3 hours. After monomer and initiator feedingwas complete, the reaction was held at temperature for an additional 30minutes. The product had a molecular weight of approximately 11,600 and92% incorporation of the tag, as measured by gel permeationchromatography (GPC) calculated from both refractive index andfluorescent detector traces using polystyrene sulfonate (PSS) MWstandards.

Polymer Example 2 Preparation of 0.04 mole % 6-VBCNB/49.98 mole %Acrylic Acid/49.98 mole % Acrylamide

[0218] A 5-neck, 1000 ml resin flask equipped with a mechanical stirrer,side baffles, reflux condenser, and nitrogen purge was charged withdeionized water (133.96 g) and heated to 65° C. with stirring (800 rpm).At temperature, initiator solution 1 (2.56 g ammonium persulfate in 30 gof deionized water), initiator solution 2 (7.74 g sodium metabisulfitein 30g of deionized water), and a monomer solution consisting of acrylicacid (88.12 g, 1.22 mole), 49.6% acrylamide (177.56 g, 1.22 mole), 50%sodium hydroxide (36.4 g, 0.455 mole), and 6-VBCNB (prepared accordingto Monomer Example 2, 0.42 g, 0.943 mmol) were added separately at aconstant flow rate over a period of 2 hours. After monomer and initiatorfeeding was complete, the reaction was held at temperature for anadditional 1 hour. The product had a molecular weight of approximately15,000 and 98% incorporation of the tag, as measured by gel permeationchromatography (GPC) calculated from both refractive index andfluorescent detector traces using polystyrene sulfonate (PSS) MWstandards.

Method of Use Example 1

[0219] Stability and Performance Testing

[0220] The fluorescence properties (excitation and emission maxima) ofpolymers prepared using the monomers are given in Table I. Excitationmaxima are all greater than 370 nm. The fluorescence of the polymersremained invariant over a pH range of approximately 2-12.

[0221] Another important feature of these polymers is the stability ofthe fluorescence in the presence of oxidizing biocides. The oxidizingbiocide stability test was performed in the following manner. Solutionsof simulated water were prepared with the desired levels of cations andanions at the desired pH. For these experiments the simulated coolingwater contained 360 ppm Ca (as CaCO₃), 200 ppm Mg (as CaCO₃), 300 ppmalkalinity (as CaCO₃) and 15 ppm of a stable phosphonate, to stabilizethe water and prevent CaCO₃ precipitation. The water was then adjustedto the desired pH with HCl or NaOH. Tests were performed at pH 7 and 9.A series of three amber bottles were labeled with the desired testsample. A 25 ml aliquot of the simulated water was delivered into eachof the three labeled bottles. To one of the bottles (labeled “B”) wasdelivered 30 μl of a 1200 ppm stock solution of bleach. To a secondbottle (labeled “S”) was delivered 30 μl of a 1200 ppm stock solution ofSTABREX® biocide, available from Nalco. To the third bottle (labeled“N”) was delivered 30 μl distilled water. The amount of free and totalchorine was measured immediately after the samples were prepared and 24hrs later at the time of fluorescence analysis. The bottles were storedfor 24 hrs in the dark. After 24 hours, fluorescence measurements weredone using the sample marked “N” as the reference sample. The %fluorescence consumed (hereinafter “% Fl consumed”) in the presence ofan oxidizing biocide was calculated as shown below. It is important tonote that lower levels of % Fl Consumed indicate lower loss offluorescent emission. Results for polymers containing the fluorescentmonomers are given in Table I.${\% \quad {F1}\quad {Consumed}} = {\frac{{{Intensity}\quad {of}\quad N\quad {Sample}} - {{Intensity}\quad {of}\quad B\quad {or}\quad S\quad {Sample}}}{{Intensity}\quad {of}\quad N\quad {Sample}} \times 100}$

TABLE I Summary of Fluorescence Properties and Oxidizing BiocideStability of a Polymer Polymer Monomer Fluorescence Oxidizing BiocideStability Example Name Properties (% Fluorescence Consumed) 1 5-ACNB  Ex= 396 nm STABREX (pH9) = 1% Em = 511 nm

[0222] When using the tagged treatment polymer as a compound of ascale-inhibitor product in an industrial water system, the only decreaseor loss of fluorescence signal from the polymer should be due to loss ofthe polymer under scaling conditions. When identifying a scaling eventas the reason for a loss of fluorescence, it is undesirable for thelevel of fluorescence to also vary based on pH changes, other componentspresent in the cooling water system, or from oxidizing biocides such asthe STABREX® biocide system.

[0223] If the amount consumed by an oxidizing biocide is equal to orless than 10% of the signal, then the tagged treatment polymer can beused in an industrial water system. Although a small amount of thetagged treatment polymer is consumed in the presence of 1 ppm STABREX®biocide, the results given above indicate that the tagged treatmentpolymers are sufficiently stable to be used in industrial water systemswhere STABREX® is present.

[0224] The specific examples herein disclosed are to be considered asbeing primarily illustrative. Various changes beyond those describedwill, no doubt, occur to those skilled in the art; such changes are tobe understood as forming a part of this invention insofar as they fallwithin the spirit and scope of the appended claims.

We claim:
 1. A fluorescent monomer selected from the group consisting ofcompounds of the formulae:

wherein R₃ is sulfonic acid and its salts or carboxylic acid and itssalts or allyloxy or vinylbenzyloxy; and R₄ is sulfonic acid and itssalts or carboxylic acid and its salts or allyloxy or vinylbenzyloxy;with the proviso that when one of R₃ or R₄ is sulfonic acid and itssalts or carboxylic acid and its salts, the other must be allyloxy orvinylbenzyloxy.
 2. A fluorescent monomer of claim 1, which is Monomer(Purple), wherein said monomer is named:5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′ benzimidazole.
 3. Afluorescent monomer of claim 1 which is6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole.
 4. Atagged treatment polymer selected from the group consisting of: (1)G_(a)Q_(j)W_(t) wherein G is selected from the group consisting of:

wherein R₃ is sulfonic acid and its salts or carboxylic acid and itssalts or allyloxy or vinylbenzyloxy; and R₄ is sulfonic acid and itssalts or carboxylic acid and its salts or allyloxy or vinylbenzyloxy;with the proviso that when one of R₃ or R₄ is sulfonic acid and itssalts or carboxylic acid and its salts, the other must be allyloxy orvinylbenzyloxy: wherein Q is selected from the group consisting ofacrylic acid and salts thereof, methacrylic acid and salts thereof,maleic acid and salts thereof, maleic anhydride, acrylamide, crotonicacid, acrylamidomethylpropane sulfonic acid and salts thereof; wherein Wis selected from the group consisting of: acrylic acid and saltsthereof, methacrylic acid and salts thereof, itaconic acid and saltsthereof, maleic acid and salts thereof, maleic anhydride, crotonic acidand salts thereof, acrylamide, methacrylamide, vinyl sulfonic acid,styrene sulfonate, N-tertbutylacrylamide, N-isopropylacrylamide,butoxymethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide,dimethylaminoethyl acrylate methyl chloride quaternary salts,dimethylaminoethyl acrylate benzyl chloride quaternary salts,dimethylaminoethyl acrylate methyl sulfate quaternary salt,dimethylaminoethyl methacrylate methyl sulfate quaternary salt,dimethylaminoethyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl methacrylamide methyl sulfate quaternary salts,diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylaminoethyl methacrylate acid salts (including, but not limited to, sulfuricacid and hydrochloride acid salts), dimethylaminoethyl methacrylatemethyl chloride quaternary salt, dimethylaminoethyl methacrylate benzylchloride quaternary salt, methacrylamidopropyl trimethyl ammoniumchloride, acrylamidopropyl trimethyl ammonium chloride, methylene bisacrylamide, triallylamine, acid salts of triallylamine, ethylene glycoldimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate,hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycoldimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycoldimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonicacid and the sodium salt thereof, vinyl alcohol, vinyl acetate, andN-vinylpyrrolidone; with the proviso that Q and W cannot both be thesame; wherein a is from about 0.001 to about 10.0 mole percent; whereinj is from about 0 to about 99.999 mole percent; wherein t is from about0 to about 99.999 mole percent; and wherein a+j+t=100; (2)G_(a)Q_(v)W_(f)S_(c) wherein G is as previously defined; wherein Q is aspreviously defined; wherein W is as previously defined, with the provisothat Q and W cannot both be the same; wherein S is selected from thegroup consisting of sulfomethylacrylamide and sulfoethylacrylamide;wherein a is from about 0.001 to about 10.00 mole percent; wherein v isfrom about 0 to about 97.999 mole percent; wherein f is from about 1 toabout 97.999 mole percent; wherein c is from about 1 to about 40 molepercent; and wherein a+v+f+c=100.
 5. A tagged treatment polymer of claim4 wherein G is 5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′benzimidazole.
 6. A tagged treatment polymer of claim 4 wherein G is6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole.
 7. Atagged treatment polymer of claim 4 wherein Q is acrylic acid and W isacrylamide.
 8. A tagged treatment polymer of claim 4 wherein Q isacrylamide, W is acrylic acid and S is N-sulfomethylacrylamide.
 9. Atagged treatment polymer of claim 4 wherein Q is acrylic acid and W isacrylamidomethylpropane sulfonic acid.
 10. A tagged treatment polymer ofclaim 4 wherein G is 5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′benzimidazole, Q is acrylic acid, W is acrylamide and S isN-sulfomethylacrylamide.
 11. A tagged treatment polymer of claim 4wherein G is6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole, Q isacrylic acid, W is acrylamide and S is N-sulfomethylacrylamide.
 12. Atagged treatment polymer of claim 4 wherein G is5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′ benzimidazole, Q isacrylic acid and W is acrylamidomethylpropane sulfonic acid.
 13. Atagged treatment polymer of claim 4 wherein G is6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole, Q isacrylic acid and W is acrylamidomethylpropane sulfonic acid.
 14. Atagged treatment polymer of claim 4 wherein G is5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′ benzimidazole and Q isacrylic acid.
 15. A tagged treatment polymer of claim 4 wherein G is6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole and Qis acrylic acid.
 16. A process for the inhibition of scale formation inan industrial water system which comprises introducing into saidindustrial water system a tagged treatment polymer selected from thegroup consisting of: (1) G_(a)Q_(j)W_(t) wherein G is selected from thegroup consisting of:

wherein R₃ is sulfonic acid and its salts or carboxylic acid and itssalts or allyloxy or vinylbenzyloxy; and R₄ is sulfonic acid and itssalts or carboxylic acid and its salts or allyloxy or vinylbenzyloxy;with the proviso that when one of R₃ or R₄ is sulfonic acid and itssalts or carboxylic acid and its salts, the other must be allyloxy orvinylbenzyloxy. wherein Q is selected from the group consisting ofacrylic acid and salts thereof, methacrylic acid and salts thereof,maleic acid and salts thereof, maleic anhydride, acrylamide, crotonicacid, acrylamidomethylpropane sulfonic acid and salts thereof; wherein Wis selected from the group consisting of: acrylic acid and saltsthereof, methacrylic acid and salts thereof, itaconic acid and saltsthereof, maleic acid and salts thereof, maleic anhydride, crotonic acidand salts thereof, acrylamide, methacrylamide, vinyl sulfonic acid,styrene sulfonate, N-tertbutylacrylamide, N-isopropylacrylamide,butoxymethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide,dimethylaminoethyl acrylate methyl chloride quaternary salts,dimethylaminoethyl acrylate benzyl chloride quaternary salts,dimethylaminoethyl acrylate methyl sulfate quaternary salt,dimethylaminoethyl methacrylate methyl sulfate quaternary salt,dimethylaminoethyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl methacrylamide methyl sulfate quaternary salts,diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylaminoethyl methacrylate acid salts (including, but not limited to, sulfuricacid and hydrochloride acid salts), dimethylaminoethyl methacrylatemethyl chloride quaternary salt, dimethylaminoethyl methacrylate benzylchloride quaternary salt, methacrylamidopropyl trimethyl ammoniumchloride, acrylamidopropyl trimethyl ammonium chloride, methylene bisacrylamide, triallylamine, acid salts of triallylamine, ethylene glycoldimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate,hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycoldimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycoldimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonicacid and the sodium salt thereof, vinyl alcohol, vinyl acetate, andN-vinylpyrrolidone; with the proviso that Q and W cannot both be thesame; wherein a is from about 0.001 to about 10.0 mole percent; whereinj is from about 0 to about 99.999 mole percent; wherein t is from about0 to about 99.999 mole percent; and wherein a+j+t=100; (2)G_(a)Q_(v)W_(f)S_(c) wherein G is as previously defined; wherein Q is aspreviously defined; wherein W is as previously defined, with the provisothat Q and W cannot both be the same; wherein S is selected from thegroup consisting of sulfomethylacrylamide and sulfoethylacrylamide;wherein a is from about 0.001 to about 10.00 mole percent; wherein v isfrom about 0 to about 97.999 mole percent; wherein f is from about 1 toabout 97.999 mole percent; wherein c is from about 1 to about 40 molepercent; and wherein a+v+f+c=100; in an amount sufficient to inhibitscale formation.
 17. The process of claim 16 wherein Q is acrylic acidand W is acrylamide.
 18. The process of claim 16 wherein Q isacrylamide, W is acrylic acid and S is N-sulfomethyl acrylamide.
 19. Theprocess of claim 16 wherein Q is acrylic acid and W isacrylamidomethylpropane sulfonic acid.
 20. The process of claim 16wherein G is 5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′benzimidazole, Q is acrylic acid, W is acrylamide and S isN-sulfomethylacrylamide.
 21. The process of claim 16 wherein G is6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole, Q isacrylic acid, W is acrylamide and S is N-sulfomethylacrylamide.
 22. Theprocess of claim 16 wherein G is5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′ benzimidazole, Q isacrylic acid and W is acrylamidomethylpropane sulfonic acid.
 23. Theprocess of claim 16 wherein G is6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole, Q isacrylic acid and W is acrylamidomethylpropane sulfonic acid.
 24. Theprocess of claim 16 wherein G is5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′ benzimidazole and Q isacrylic acid.
 25. The process of claim 16 wherein G is6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole and Qis acrylic acid.
 26. A method for maintaining the desired amount oftagged treatment polymer in an industrial water system comprising thesteps of: i) adding to said industrial water system a tagged treatmentpolymer, selected from a group consisting of: (1) G_(a)Q_(j)W_(t)wherein G is selected from the group consisting of:

wherein R₃ is sulfonic acid and its salts or carboxylic acid and itssalts or allyloxy or vinylbenzyloxy; and R₄ is sulfonic acid and itssalts or carboxylic acid and its salts or allyloxy or vinylbenzyloxy;with the proviso that when one of R₃ or R₄ is sulfonic acid and itssalts or carboxylic acid and its salts, the other must be allyloxy orvinylbenzyloxy; wherein Q is selected from the group consisting ofacrylic acid and salts thereof, methacrylic acid and salts thereof,maleic acid and salts thereof, maleic anhydride, acrylamide, crotonicacid, acrylamidomethylpropane sulfonic acid and salts thereof; wherein Wis selected from the group consisting of: acrylic acid and saltsthereof, methacrylic acid and salts thereof, itaconic acid and saltsthereof, maleic acid and salts thereof, maleic anhydride, crotonic acidand salts thereof, acrylamide, methacrylamide, vinyl sulfonic acid,styrene sulfonate, N-tertbutylacrylamide, N-isopropylacrylamide,butoxymethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide,dimethylaminoethyl acrylate methyl chloride quaternary salts,dimethylaminoethyl acrylate benzyl chloride quaternary salts,dimethylaminoethyl acrylate methyl sulfate quaternary salt,dimethylaminoethyl methacrylate methyl sulfate quaternary salt,dimethylaminoethyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl methacrylamide methyl sulfate quaternary salts,diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylaminoethyl methacrylate acid salts (including, but not limited to, sulfuricacid and hydrochloride acid salts), dimethylaminoethyl methacrylatemethyl chloride quaternary salt, dimethylaminoethyl methacrylate benzylchloride quaternary salt, methacrylamidopropyl trimethyl ammoniumchloride, acrylamidopropyl trimethyl ammonium chloride, methylene bisacrylamide, triallylamine, acid salts of triallylamine, ethylene glycoldimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate,hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycoldimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycoldimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonicacid and the sodium salt thereof, vinyl alcohol, vinyl acetate, andN-vinylpyrrolidone; with the proviso that Q and W cannot both be thesame; wherein a is from about 0.001 to about 10.0 mole percent; whereinj is from about 0 to about 99.999 mole percent; wherein t is from about0 to about 99.999 mole percent; and wherein a+j+t=100; (2)G_(a)Q_(v)W_(f)S_(c) wherein G is as previously defined; wherein Q is aspreviously defined; wherein W is as previously defined, with the provisothat Q and W cannot both be the same; wherein S is selected from thegroup consisting of sulfomethylacrylamide and sulfoethylacrylamide;wherein a is from about 0.001 to about 10.00 mole percent; wherein v isfrom about 0 to about 97.999 mole percent; wherein f is from about 1 toabout 97.999 mole percent; wherein c is from about 1 to about 40 molepercent; and wherein a+v+f+c=100; ii) using a fluorometer to detect thefluorescent signal of said tagged treatment polymer; iii) converting thefluorescent signal of said tagged treatment polymer to the concentrationof said tagged treatment polymer; and iv) adjusting the concentration ofsaid tagged treatment polymer according to what the desiredconcentration is for said tagged treatment polymer in said industrialwater system.
 27. The method of claim 26 wherein Q is acrylic acid and Wis acrylamide.
 28. The method of claim 26 wherein Q is acrylamide, W isacrylic acid and S is N-sulfomethylacrylamide.
 29. The method of claim26 wherein Q is acrylic acid and W is acrylamidomethylpropane sulfonicacid.
 30. The method of claim 26 wherein G is5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′ benzimidazole, Q isacrylic acid, W is acrylamide and S is N-sulfomethylacrylamide.
 31. Themethod of claim 26 wherein G is6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole, Q isacrylic acid, W is acrylamide and S is N-sulfomethylacrylamide.
 32. Themethod of claim 26 wherein said fluorescent monomer G is5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′ benzimidazole, Q isacrylic acid and W is acrylamidomethylpropane sulfonic acid.
 33. Themethod of claim 26 wherein said fluorescent monomer G is6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole, Q isacrylic acid and W is acrylamidomethylpropane sulfonic acid.
 34. Themethod of claim 26 wherein said fluorescent monomer G is5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′ benzimidazole and Q isacrylic acid.
 35. The method of claim 26 wherein said fluorescentmonomer G is6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole and Qis acrylic acid.
 36. A method for maintaining the desired amount oftagged treatment polymer in an industrial water system comprising thesteps of: a) adding an inert tracer and a tagged treatment polymer tothe water of an industrial water system, wherein said tagged treatmentpolymer is selected from the group consisting of: (1) G_(a)Q_(j)W_(t)wherein G is selected from the group consisting of:

wherein R₃ is sulfonic acid and its salts or carboxylic acid and itssalts or allyloxy or vinylbenzyloxy; and R₄ is sulfonic acid and itssalts or carboxylic acid and its salts or allyloxy or vinylbenzyloxy;with the proviso that when one of R₃ or R₄ is sulfonic acid and itssalts or carboxylic acid and its salts, the other must be allyloxy orvinylbenzyloxy. wherein Q is selected from the group consisting ofacrylic acid and salts thereof, methacrylic acid and salts thereof,maleic acid and salts thereof, maleic anhydride, acrylamide, crotonicacid, acrylamidomethylpropane sulfonic acid and salts thereof; wherein Wis selected from the group consisting of: acrylic acid and saltsthereof, methacrylic acid and salts thereof, itaconic acid and saltsthereof, maleic acid and salts thereof, maleic anhydride, crotonic acidand salts thereof, acrylamide, methacrylamide, vinyl sulfonic acid,styrene sulfonate, N-tertbutylacrylamide, N-isopropylacrylamide,butoxymethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide,dimethylaminoethyl acrylate methyl chloride quaternary salts,dimethylaminoethyl acrylate benzyl chloride quaternary salts,dimethylaminoethyl acrylate methyl sulfate quaternary salt,dimethylaminoethyl methacrylate methyl sulfate quaternary salt,dimethylaminoethyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl methacrylamide methyl sulfate quaternary salts,diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylaminoethyl methacrylate acid salts (including, but not limited to, sulfuricacid and hydrochloride acid salts), dimethylaminoethyl methacrylatemethyl chloride quaternary salt, dimethylaminoethyl methacrylate benzylchloride quaternary salt, methacrylamidopropyl trimethyl ammoniumchloride, acrylamidopropyl trimethyl ammonium chloride, methylene bisacrylamide, triallylamine, acid salts of triallylamine, ethylene glycoldimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate,hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycoldimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycoldimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonicacid and the sodium salt thereof, vinyl alcohol, vinyl acetate, andN-vinylpyrrolidone; with the proviso that Q and W cannot both be thesame; wherein a is from about 0.001 to about 10.0 mole percent; whereinj is from about 0 to about 99.999 mole percent; wherein t is from about0 to about 99.999 mole percent; and wherein a+j+t=100; (2)G_(a)Q_(v)W_(f)S_(c) wherein G is as previously defined; wherein Q is aspreviously defined; wherein W is as previously defined, with the provisothat Q and W cannot both be the same; wherein S is selected from thegroup consisting of sulfomethylacrylamide and sulfoethylacrylamide;wherein a is from about 0.001 to about 10.00 mole percent; wherein v isfrom about 0 to about 97.999 mole percent; wherein f is from about 1 toabout 97.999 mole percent; wherein c is from about 1 to about 40 molepercent; and wherein a+v+f+c=100; such that a desired concentration ofsaid tagged treatment polymer is present in said water; b) using afluorometer to detect the fluorescent signals of said inert tracer andsaid tagged treatment polymer; c) converting the fluorescent signals ofsaid inert tracer and said tagged treatment polymer to the concentrationof said inert tracer and said tagged treatment polymer; and d) adjustingthe concentration of said tagged treatment polymer according to what thedesired concentration is for said tagged treatment polymer in saidindustrial water system.
 37. The method of claim 36 wherein Q is acrylicacid and W is acrylamide.
 38. The method of claim 36 wherein Q isacrylamide, W is acrylic acid and S is N-sulfomethyl acrylamide.
 39. Themethod of claim 36 wherein Q is acrylic acid and W isacrylamidomethylpropane sulfonic acid.
 40. The method of claim 36wherein G is 5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′benzimidazole, Q is acrylic acid, W is acrylamide and S isN-sulfomethylacrylamide.
 41. The method of claim 36 wherein G is6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole, Q isacrylic acid, W is acrylamide and S is N-sulfomethylacrylamide.
 42. Themethod of claim 36 wherein G is5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′ benzimidazole, Q isacrylic acid and W is acrylamidomethylpropane sulfonic acid.
 43. Themethod of claim 36 wherein G is6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole, Q isacrylic acid and W is acrylamidomethylpropane sulfonic acid.
 44. Themethod of claim 36 wherein G is5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′ benzimidazole and Q isacrylic acid.
 45. The method of claim 36 wherein G is6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole, and Qis acrylic acid.